Amorphous polycarbonate films for capacitors, methods of manufacture, and articles manufactured therefrom

ABSTRACT

A uniaxially-stretched, extruded film comprising a polycarbonate, wherein the extruded film has at least one wrinkle-free region having a first surface and a second surface, the at least one extruded wrinkle-free region comprising: an extruded thickness of more than 0 and less than 7 micrometer, and a variation of the thickness of the film of +/−10% of the thickness of the film, and a surface roughness average that is less than +/−3% of the average thickness of the film as measured by optional profilometery; and further wherein the film has a dielectric constant at 1 kHz and room temperature of at least 2.7; a dissipation factor at 1 kHz and room temperature of 1% or less; and a breakdown strength of at least 300 Volt/micrometer.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/485,305 filed May 12, 2011. The relatedapplication is incorporated herein by reference.

BACKGROUND OF THE INVENTION

This disclosure relates to polymer films, and in particular to amorphouspolymer films useful for the manufacture of capacitors.

Electrostatic film capacitors with high volumetric energy density, highoperating temperature, and long lifetime are critical components forpulse-power, automotive, and industrial electronics. Capacitors areessentially energy-storing devices having two parallel conductive platesseparated by a thin layer of an insulating (dielectric) film. When avoltage is applied across the plates, the electric field in thedielectric displaces electric charges, and thus stores energy. Theamount of energy stored by a capacitor depends on the dielectricconstant and breakdown voltage of the insulating material, and thedimensions (total area and thickness) of the film, such that in order tomaximize the total amount of energy that a capacitor can accumulate, thedielectric constant and breakdown voltage of the film are maximized, andthe thickness of the film minimized. Because the physicalcharacteristics of the dielectric material in the capacitor are theprimary determining factors for the performance of a capacitor,improvements in one or more of the physical properties of the dielectricmaterial in a capacitor can result in corresponding performanceimprovements in the capacitor component, usually resulting inperformance and lifetime enhancements of the electronics system orproduct in which it is embedded.

Electrostatic film capacitors made from biaxially-orientedpoly(propylene) (BOPP) have been used in applications requiring a lowdissipation factor, high insulation resistance and low dielectricabsorption, such as in electrical appliances, electronic equipment, ovenand furnaces, refrigerators, automobiles, and home appliances. The lowdielectric constant (Dk), which is about 2.2, and the maximum servicetemperature of about 100° C., limits the use of these capacitors inapplications requiring high operating temperatures and/or high energydensities. Poly(carbonate) (also known as polycarbonate, or PC) filmshave a higher dielectric constant than BOPP films (about 3.0) and ahigher maximum service temperature of about 125° C.

There accordingly remains a need in the art for new films and methodsfor their manufacture that can produce films of very high purity andwith excellent electrical properties, in particular high breakdownstrength, and high dielectric constant. It would be a further advantageif such films could operate at higher temperature than BOPP films. Thereremains a further need for efficient methods for producing such filmsthat are amendable to industrial scale processes. It would be furtheradvantage if such methods were environmentally friendly.

SUMMARY OF THE INVENTION

The invention relates to a uniaxially-stretched, extruded filmcomprising a polycarbonate, wherein the film has at least onewrinkle-free region having a first surface and a second surface, the atleast one extruded wrinkle-free region comprising: a thickness of morethan 0 and less than 7 micrometers, and a variation of the thickness ofthe film of +/−10% or less of the thickness of the film, and a surfaceroughness average of less than +/−3% of the average thickness of thefilm as measured by optical profilometry; and further wherein the filmhas: a dielectric constant at 1 kHz and room temperature of at least2.7; a dissipation factor at 1 kHz and room temperature of 1% or less;and a breakdown strength of at least 300 Volts/micrometer.

Articles comprising the above compositions are also disclosed.

In another embodiment, our invention relates to metallizeduniaxially-stretched, extruded films.

In another embodiment, our invention relates to capacitors made frommetallized uniaxially-stretched, extruded films.

In another embodiment, our invention relates to an electronic articlecomprising the capacitors made from wound metallizeduniaxially-stretched extruded film.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have discovered that polycarbonate substrate filmsfor electrostatic capacitors having excellent properties can bemanufactured in a solventless process by extrusion. In a surprising andimportant feature, the extruded films can have large wrinkle-freeregions having a breakdown strength of at least 300 Volts/micrometer.The wrinkle-free regions are sufficiently smooth and flat such that thesubstrate film can be metallized to provide a metallized film ofsubstantially uniform breakdown strength across the region.

In particular, the wrinkle-free regions have a thickness of more than 0and less than 7 micrometers, where any variation of the thickness of thefilm is ±10% of the average thickness of the film, and the surfaceroughness of the film is less than 3% of the average thickness of thefilm. The films provide both an increase in the capacitor dielectricconstant and dielectric breakdown strength compared to prior art films,while retaining other advantageous physical and electricalcharacteristics, such as flexibility, thinness, and dielectric constantstability. In particular, the films can have a high voltage breakdownstrength (at least 300 Volts/micrometer), a high dielectric constant(greater than 2.7), and a low dissipation factor (less than 1%). Thefilms and capacitors made from the films accordingly offer advantagesover current materials and methods for the manufacture of components forthe electronics industry. A particular advantage is that the films canbe reliably manufactured on an industrial scale in a solventlessprocess. Removal of solvent from solvent-cast films can be difficult.The extruded films herein are processed without solvent, providing botha cost and a manufacturing advantage. In another embodiment, theextruded films are more than 0 and less than or equal to 13 microns.

Various numerical ranges are disclosed in this patent application.Because these ranges are continuous, they include every value betweenthe minimum and maximum values. Unless expressly indicated otherwise,the various numerical ranges specified in this application areapproximations. The endpoints of all ranges directed to the samecomponent or property are inclusive of the endpoint and independentlycombinable.

All molecular weights in this application refer to weight averagemolecular weights unless indicated otherwise. All such mentionedmolecular weights are expressed in Daltons.

The terms “a” and “an” do not denote a limitation of quantity, butrather denote the presence of at least one of the referenced items. Asused herein, “combination thereof” is inclusive of one or more of therecited elements, optionally together with a like element not recited.Reference throughout the specification to “an embodiment,” “anotherembodiment,” “an embodiment,” “some embodiments,” and so forth, meansthat a particular element (e.g., feature, structure, property, and/orcharacteristic) described in connection with the embodiment is includedin at least an embodiment described herein, and can or cannot be presentin other embodiments. In addition, it is to be understood that thedescribed element(s) can be combined in any suitable manner in thevarious embodiments.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. The term “alkyl” includes bothC₁₋₃₀ branched and straight chain, unsaturated aliphatic hydrocarbongroups having the specified number of carbon atoms. Examples of alkylinclude, but are not limited to, methyl, ethyl, n-propyl, i-propyl,n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n- ands-heptyl, and, n- and s-octyl. The term “aryl” means an aromatic moietycontaining the specified number of carbon atoms, such as to phenyl,tropone, indanyl, or naphthyl.

All ASTM tests are based on the 2003 edition of the Annual Book of ASTMStandards unless otherwise indicated.

The polycarbonate can be a polycarbonate homopolymer or a polycarbonatecopolymer as further described below. Polycarbonates are polymers havingrepeating structural carbonate units (1)

in which at least 60 percent of the total number of R¹ groups containaromatic moieties and the balance thereof are aliphatic, alicyclic, oraromatic. In an embodiment, each R¹ is a C₆₋₃₀ aromatic group, that is,contains at least one aromatic moiety. R¹ can be derived from anaromatic dihydroxy compound of the formula HO—R¹—OH, in particular (2)

HO-A¹-Y¹-A²-OH  (2)

wherein each of A¹ and A² is a monocyclic divalent aromatic group and Y¹is a single bond or a bridging group having one or more atoms thatseparate A¹ from A². In an exemplary embodiment, one atom separates A¹from A². Also included are bisphenol compounds (3)

wherein R^(a) and R^(b) are each independently a halogen atom or amonovalent hydrocarbon group and may be the same or different; p and qare each independently integers of 0 to 4; and X^(a) is a bridging groupconnecting the two hydroxy-substituted aromatic groups, where thebridging group and the hydroxy substituent of each C₆ arylene group aredisposed ortho, meta, or para (specifically para) to each other on theC₆ arylene group. In an embodiment, the bridging group X^(a) is a singlebond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organic group. TheC₁₋₁₈ organic bridging group can be cyclic or acyclic, aromatic ornon-aromatic, and can further comprise heteroatoms such as a halogen,oxygen, nitrogen, sulfur, silicon, or phosphorous. The C₁₋₁₈ organicgroup can be disposed such that the C₆ arylene groups connected theretoare each connected to a common alkylidene carbon or to different carbonsof the C₁₋₁₈ organic bridging group. In particular, X^(a) is a C₁₋₁₈alkylene group, a C₃₋₁₈ cycloalkylene group, a fused C₆₋₁₈ cycloalkylenegroup, or a group of the formula —B¹—W—B²— wherein B¹ and B² are thesame or different C₁₋₆ alkylene group and W is a C₃₋₁₂ cycloalkylidenegroup or a C₆₋₁₆ arylene group.

Exemplary C₁₋₁₈ organic bridging groups include methylene,cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, aswell as 2-[2.2.1]-bicycloheptylidene and cycloalkylidenes such ascyclohexylidene, cyclopentylidene, cyclododecylidene, andadamantylidene. A specific example of bisphenol (3) wherein X^(a) is asubstituted cycloalkylidene is the cyclohexylidene-bridged,alkyl-substituted bisphenol (4)

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, R^(g) isC₁₋₁₂ alkyl or halogen, r and s are each independently 1 to 4, and t is0 to 10. In a specific embodiment, at least one of each of R^(a′) andR^(b′) is disposed meta to the cyclohexylidene bridging group. Thesubstituents R^(a′), R^(b′), and R^(g) can, when comprising anappropriate number of carbon atoms, be a straight chain, cyclic,bicyclic, branched, saturated, or unsaturated. In an embodiment, R^(a′)and R^(b′) are each independently C₁₋₄ alkyl, R^(g) is C₁₋₄ alkyl, r ands are each 1, and t is 0 to 5. In another specific embodiment, R^(a′),R^(b′) and R^(g) are each methyl, r and s are each 1, and t is 0 or 3.In another exemplary embodiment, the cyclohexylidene-bridged bisphenolis the reaction product of two moles of a cresol with one mole of ahydrogenated isophorone (e.g., 1,1,3-trimethyl-3-cyclohexane-5-one).

X^(a) in bisphenol (3) can also be a substituted C₃₋₁₈ cycloalkylidene(5)

wherein R^(r), R^(p), R^(q), and R^(t) are independently hydrogen,halogen, oxygen, or C₁₋₁₂ organic groups; I is a direct bond, a carbon,or a divalent oxygen, sulfur, or —N(Z)— where Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 1or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with theproviso that at least two of R^(r), R^(p), R^(q), and R^(t) takentogether are a fused cycloaliphatic, aromatic, or heteroaromatic ring.It will be understood that when the fused ring is aromatic, the ring asshown in formula (5) will have an unsaturated carbon-carbon linkagewhere the ring is fused. When k is one and i is 0, the ring as shown informula (5) contains 4 carbon atoms, when k is 2, the ring as shown informula (5) contains 5 carbon atoms, and when k is 3, the ring contains6 carbon atoms. In an embodiment, two adjacent groups (e.g., R^(q) andR^(t) taken together) form an aromatic group, and in another embodiment,R^(q) and R^(t) taken together form one aromatic group and R^(r) andR^(p) taken together form a second aromatic group. When R^(q) and R^(t)taken together form an aromatic group, R^(p) can be a double-bondedoxygen atom, i.e., a ketone.

In another specific embodiment of the bisphenol compound (3), the C₁₋₁₈organic bridging group includes groups —C(R^(c))(R^(d))— or —C(═R^(e))—,wherein R^(c) and R^(d) are each independently a hydrogen atom or amonovalent C₁₋₆ linear or cyclic hydrocarbon group and R^(e) is adivalent hydrocarbon group, p and q is each 0 or 1, and R^(a) and R^(b)are each a C₁₋₃ alkyl group, specifically methyl, disposed meta to thehydroxy group on each arylene group.

Other useful aromatic dihydroxy compounds of the formula HO—R¹—OHinclude aromatic dihydric compounds (6)

wherein each R^(h) is independently a halogen atom, a C₁₋₁₀ hydrocarbylsuch as a C₁₋₁₀ alkyl group, a halogen-substituted C₁₋₁₀ alkyl group, aC₆₋₁₀ aryl group, or a halogen-substituted C₆₋₁₀ aryl group, and n is 0to 4. The halogen is usually bromine.

Some illustrative examples of specific aromatic dihydroxy compoundsinclude the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantane, alpha,alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalimide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compoundssuch as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol,5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromoresorcinol, or the like; catechol; hydroquinone; substitutedhydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone,2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like, orcombinations comprising at least one of the foregoing dihydroxycompounds.

Specific examples of bisphenol compounds (3) include1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl) propane (also known as “bisphenol A” or “BPA”),2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-2-methylphenyl) propane,1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP),and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinationscomprising at least one of the foregoing dihydroxy compounds can also beused. In one specific embodiment, the polycarbonate is a linearhomopolymer derived from bisphenol A, in which each of A¹ and A² isp-phenylene and Y¹ is isopropylidene in formula (13).

“Polycarbonate” as used herein includes homopolycarbonates (wherein eachR¹ in the polymer is the same), copolymers comprising different R¹moieties in the carbonate units (referred to herein as“copolycarbonates”), copolymers comprising carbonate units and othertypes of polymer units (such as ester units, diorganosiloxane units,urethane units, arylene ether units, arylene sulfone units, aryleneketone units, and combinations thereof), and combinations of at leastone homopolycarbonate and/or at least one copolycarbonate and/or atleast one polycarbonate copolymer. As used herein, a “combination” isinclusive of blends, mixtures, alloys, reaction products, and the like.

A specific polycarbonate copolymer is a poly(carbonate-ester). Suchcopolymers further contain, in addition to repeating carbonate units(1), repeating ester units (7)

wherein J is a divalent group derived from a dihydroxy compound, and canbe, for example, a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclic group, aC₆₋₂₀ aromatic group or a polyoxyalkylene group in which the alkylenegroups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbonatoms; and T divalent group derived from a dicarboxylic acid, and canbe, for example, a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclic group, aC₆₋₂₀ alkyl aromatic group, or a C₆₋₂₀ aromatic group.Poly(carbonate-ester)s containing a combination of different T and/or Jgroups can be used. The poly(carbonate-ester)s can be branched orlinear.

In an embodiment, J is a C₂₋₃₀ alkylene group having a straight chain,branched chain, or cyclic (including polycyclic) structure. In anotherembodiment, J is derived from an aromatic dihydroxy compound (3). Inanother embodiment, J is derived from an aromatic dihydroxy compound(4). In another embodiment, J is derived from an aromatic dihydroxycompound (6).

Exemplary aromatic dicarboxylic acids that can be used to prepare thepolyester units include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids include terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or acombination comprising at least one of the foregoing acids. A specificdicarboxylic acid comprises a combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98. In another specific embodiment, J isa C₂₋₆ alkylene group and T is p-phenylene, m-phenylene, naphthalene, adivalent cycloaliphatic group, or a combination thereof.

The molar ratio of carbonate units to ester units in the copolymers canvary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10,more specifically 25:75 to 75:25, depending on the desired properties ofthe final composition.

A specific embodiment of a poly(carbonate-ester) (8) comprises repeatingaromatic carbonate and aromatic ester units

wherein Ar is divalent aromatic residue of a dicarboxylic acid orcombination of dicarboxylic acids, and Ar′ is a divalent aromaticresidue of a bisphenol (3) or a dihydric compound (6). Ar is thus anaryl group, and is preferably the residue of isophthalic acid (9a),terephthalic acid (9b),

or a combination thereof. Ar′ may be polycyclic, e.g., a residue ofbiphenol or bisphenol A, or monocyclic, e.g., the residue ofhydroquinone or resorcinol.

Further in the poly(carbonate-ester) (8), x and y represent therespective parts by weight of the aromatic ester units and the aromaticcarbonate units based on 100 parts total weight of the copolymer.Specifically, x, the aromatic ester content, is 20 to less than 100 wt.%, specifically 30 to 95 wt. %, still more specifically 50 to 95 wt. %,and y, the carbonate content, is from more than zero to 80 wt. %, from 5to 70 wt. %, still more specifically from 5 to 50 wt. %, each based onthe total weight of units x+y. In general, any aromatic dicarboxylicacid conventionally used in the preparation of polyesters may beutilized in the preparation of poly(carbonate-ester)s (8) butterephthalic acid alone can be used, or mixtures thereof withisophthalic acid wherein the weight ratio of terephthalic acid toisophthalic acid is in the range of from 5:95 to 95:5.Poly(carbonate-ester)s (8) comprising 35 to 45 wt. % of carbonate unitsand 55 to 65 wt. % of ester units, wherein the ester units have a molarratio of isophthalate to terephthalate of 45:55 to 55:45 are oftenreferred to as poly(carbonate-ester)s (PCE) and copolymers comprising 15to 25 wt. % of carbonate units and 75 to 85 wt. % of ester units havinga molar ratio of isophthalate to terephthalate from 98:2 to 88:12 areoften referred to as poly(phthalate-carbonate)s (PPC). In theseembodiments the PCE or PPC (8) can be derived from the reaction ofbisphenol-A and phosgene with iso- and terephthaloyl chloride, and canhave an intrinsic viscosity of 0.5 to 0.65 deciliters per gram (measuredin methylene chloride at a temperature of 25° C.).

In another specific embodiment, a poly(carbonate-ester) comprisescarbonate units (1) derived from a bisphenol compound (3), and esterunits derived from an aromatic dicarboxylic acid and dihydroxy compound(6). Specifically, the ester units are arylate ester units (9)

wherein each R⁴ is independently a halogen or a C₁₋₄ alkyl, and p is 0to 3. The arylate ester units (9) can be derived from the reaction of amixture of terephthalic acid and isophthalic acid or chemicalequivalents thereof with compounds such as 5-methyl resorcinol, 5-ethylresorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butylresorcinol, 2,4,5-trifluoro resorcinol, 2,4,6-trifluoro resorcinol,4,5,6-trifluoro resorcinol, 2,4,5-tribromo resorcinol, 2,4,6-tribromoresorcinol, 4,5,6-tribromo resorcinol, catechol, hydroquinone, 2-methylhydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butylhydroquinone, 2-t-butyl hydroquinone, 2,3,5-trimethyl hydroquinone,2,3,5-tri-t-butyl hydroquinone, 2,3,5-trifluoro hydroquinone,2,3,5-tribromo hydroquinone, or a combination comprising at least one ofthe foregoing compounds. The arylate ester units (8) can bepoly(isophthalate-terephthalate-resorcinol ester) units, also known as“ITR” esters.

The poly(carbonate-ester)s comprising arylate ester units (9) cancomprise, based on the total weight of the copolymer, from 1 to lessthan 100 wt. %, 10 to less than 100 wt. %, 20 to less than 100 wt. %, or40 to less than 100 wt. % of carbonate units (1) derived from abisphenol compound (3), and from greater than 0 to 99 wt. %, greaterthan 0 to 90 wt. %, greater than 0 to 80 wt. %, or greater than 0 to 60wt. % of ester units derived from an aromatic dicarboxylic acid anddihydroxy compound (6). A specific poly(carbonate-ester) comprisingarylate ester units (9) is a poly(bisphenol-Acarbonate)-co-poly(isophthalate-terephthalate-resorcinol ester).

In another specific embodiment, the poly(carbonate-ester) containscarbonate units (1) derived from a combination of a bisphenol (3) and anaromatic dihydric compound (6), and arylate ester units (9). The molarratio of carbonate units derived from bisphenol (3) to carbonate unitsderived from aromatic dihydric compound (6) can be 1:99 to 99:1. Aspecific poly(carbonate-ester) of this type is a poly(bisphenol-Acarbonate)-co-(resorcinolcarbonate)-co(isophthalate-terephthalate-resorcinol ester).

The polycarbonates can further comprise siloxane units, for example apoly(carbonate-siloxane) or a poly(carbonate-ester-siloxane). Thesiloxane units are present in the copolymer in polysiloxane blocks,which comprise repeating siloxane units (10)

wherein each R is independently the same or different C₁₋₁₃ monovalentorganic group. For example, R can be a C₁-C₁₃ alkyl, C₁-C₁₃ alkoxy,C₂-C₁₃ alkenyl group, C₂-C₁₃ alkenyloxy, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₆-C₁₄ aryl, C₆-C₁₀ aryloxy, C₇-C₁₃ arylalkyl, C₇-C₁₃aralkoxy, C₇-C₁₃ alkylaryl, or C₇-C₁₃ alkylaryloxy. The foregoing groupscan be fully or partially halogenated with fluorine, chlorine, bromine,or iodine, or a combination thereof. In an embodiment, where atransparent polysiloxane-polycarbonate is desired, R is unsubstituted byhalogen. Combinations of the foregoing R groups can be used in the samecopolymer.

The value of E in formula (10) can vary depending on the type andrelative amount of each component in the composition, the desiredproperties of the, and like considerations. Generally, E has an averagevalue of 5 to 50, specifically 5 to about 40, more specifically 10 to30. A combination of a first and a second (or more) copolymers can beused, wherein the average value of E of the first copolymer is less thanthe average value of E of the second copolymer.

In an embodiment, the polysiloxane blocks are of formula (11) or (12)

wherein E is as defined in siloxane (10) and each R can be the same ordifferent, and is as defined in siloxane (1). Each Ar in blocks (11) and(12) can be the same or different, and is a substituted or unsubstitutedC₆-C₃₀ arylene group, wherein the bonds are directly connected to anaromatic moiety. The Ar groups in (11) can be derived from a bisphenol(3), for example 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) propane,2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-1-methylphenyl) propane,1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising atleast one of the foregoing compounds can also be used. Each R⁵ informula (12) is independently a divalent C₁-C₃₀ organic group, forexample a divalent C₂-C₈ aliphatic group.

In a specific embodiment, the polysiloxane blocks are of formula (13):

wherein R and E are as defined in formula (10); R⁶ is a divalent C₂-C₈aliphatic group; each M is independently a halogen, cyano, nitro, C₁-C₈alkylthio, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxygroup, C₃-C₈ cycloalkyl, C₃-C₈ cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy,C₇-C₁₂ aralkyl, C₇-C₁₂ aralkoxy, C₇-C₁₂ alkylaryl, or C₇-C₁₂alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4. In anembodiment, M is bromo or chloro, an alkyl group such as methyl, ethyl,or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or anaryl group such as phenyl, chlorophenyl, or tolyl; R² is a dimethylene,trimethylene or tetramethylene group; and R is a C₁₋₈ alkyl, haloalkylsuch as trifluoropropyl, cyanoalkyl, or C₆₋₈ aryl such as phenyl,chlorophenyl or tolyl. In another embodiment, R is methyl, or acombination of methyl and trifluoropropyl, or a combination of methyland phenyl. In still another embodiment, M is methoxy, n is one, R² is adivalent C₁-C₃ aliphatic group, and R is methyl.

In an embodiment, the polycarbonate is a poly(carbonate-siloxane) whichcomprises carbonate units (1) derived from a bisphenol (3), specificallybisphenol A, and siloxane units (13) wherein M is methoxy, n is one, R²is a divalent C₁-C₃ aliphatic group, and R is methyl. Thepoly(carbonate-siloxane)s can comprise 50 to 99 wt. % of carbonate unitsand 1 to 50 wt. % siloxane units. Within this range, thepoly(carbonate-siloxane)s can comprise 70 to 98 wt. %, more specifically75 to 97 wt. % of carbonate units and 2 to 30 wt. %, more specifically 3to 25 wt. % siloxane units.

In another embodiment, the polycarbonate is apoly(carbonate-ester-siloxane) which comprises carbonate units (1)derived from a bisphenol (3), specifically bisphenol A; siloxane units(13) wherein M is methoxy, n is one, R² is a divalent C₁-C₃ aliphaticgroup, and R is methyl and ester units (9), specifically(isophthalate-terephthalate-resorcinol) ester units.

Polycarbonates can be manufactured by processes such as interfacialpolymerization and melt polymerization. Although the reaction conditionsfor interfacial polymerization can vary, an exemplary process generallyinvolves dissolving or dispersing a dihydric phenol reactant in aqueouscaustic soda or potash, adding the resulting mixture to awater-immiscible solvent medium, and contacting the reactants with acarbonate precursor in the presence of a catalyst such as triethylamineand/or a phase transfer catalyst, under controlled pH conditions, e.g.,8 to 12. The most commonly used water immiscible solvents includemethylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, and thelike.

Exemplary carbonate precursors include a carbonyl halide such ascarbonyl bromide or carbonyl chloride, or a haloformate such as abishaloformates of a dihydric phenol (e.g., the bischloroformates ofbisphenol A, hydroquinone, or the like) or a glycol (e.g., thebishaloformate of ethylene glycol, neopentyl glycol, polyethyleneglycol, or the like). Combinations comprising at least one of theforegoing types of carbonate precursors can also be used. In anexemplary embodiment, an interfacial polymerization reaction to formcarbonate linkages uses phosgene as a carbonate precursor, and isreferred to as a phosgenation reaction.

Among the phase transfer catalysts that can be used are catalysts of theformula (R³)₄Q⁺X, wherein each R³ is the same or different, and is aC₁₋₁₀ alkyl group; Q is a nitrogen or phosphorus atom; and X is ahalogen atom or a C₁₋₈ alkoxy group or C₆₋₁₈ aryloxy group. Exemplaryphase transfer catalysts include, for example, [CH₃(CH₂)₃]₄NX,[CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX,CH₃[CH₃(CH₂)₃]₃NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈alkoxy group or a C₆₋₁₈ aryloxy group. An effective amount of a phasetransfer catalyst can be 0.1 to 10 wt. % based on the weight ofbisphenol in the phosgenation mixture. In another embodiment aneffective amount of phase transfer catalyst can be 0.5 to 2 wt. % basedon the weight of bisphenol in the phosgenation mixture.

All types of polycarbonate end groups are contemplated as being usefulin the polycarbonate composition, provided that such end groups do notsignificantly adversely affect desired properties of the compositions.

Branched polycarbonate blocks can be prepared by adding a branchingagent during polymerization. These branching agents includepolyfunctional organic compounds containing at least three functionalgroups selected from hydroxyl, carboxyl, carboxylic anhydride,haloformyl, and mixtures of the foregoing functional groups. Specificexamples include trimellitic acid, trimellitic anhydride, trimellitictrichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol,tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene),tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents can be added ata level of 0.05 to 2.0 wt. %. Mixtures comprising linear polycarbonatesand branched polycarbonates can be used.

A chain stopper (also referred to as a capping agent) can be includedduring polymerization. The chain stopper limits molecular weight growthrate, and so controls molecular weight in the polycarbonate. Exemplarychain stoppers include certain mono-phenolic compounds, mono-carboxylicacid chlorides, and/or mono-chloroformates. Mono-phenolic chain stoppersare exemplified by monocyclic phenols such as phenol and C₁-C₂₂alkyl-substituted phenols such as p-cumyl-phenol, resorcinolmonobenzoate, and p- and tertiary-butyl phenol; and monoethers ofdiphenols, such as p-methoxyphenol. Alkyl-substituted phenols withbranched chain alkyl substituents having 8 to 9 carbon atom can bespecifically mentioned. Certain mono-phenolic UV absorbers can also beused as a capping agent, for example4-substituted-2-hydroxybenzophenones and their derivatives, arylsalicylates, monoesters of diphenols such as resorcinol monobenzoate,2-(2-hydroxyaryl)-benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like.

Mono-carboxylic acid chlorides can also be used as chain stoppers. Theseinclude monocyclic, mono-carboxylic acid chlorides such as benzoylchloride, C₁-C₂₂ alkyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and combinations thereof;polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydridechloride, and naphthoyl chloride; and combinations of monocyclic andpolycyclic mono-carboxylic acid chlorides. Chlorides of aliphaticmonocarboxylic acids with less than or equal to 22 carbon atoms areuseful. Functionalized chlorides of aliphatic monocarboxylic acids, suchas acryloyl chloride and methacryoyl chloride, are also useful. Alsouseful are mono-chloroformates including monocyclic,mono-chloroformates, such as phenyl chloroformate, alkyl-substitutedphenyl chloroformate, p-cumyl phenyl chloroformate, toluenechloroformate, and combinations thereof.

Alternatively, melt processes can be used to make the polycarbonates.Generally, in the melt polymerization process, polycarbonates can beprepared by co-reacting, in a molten state, the dihydroxy reactant(s)and a diaryl carbonate ester, such as diphenyl carbonate, in thepresence of a transesterification catalyst in a Banbury® mixer, twinscrew extruder, or the like to form a uniform dispersion. Volatilemonohydric phenol is removed from the molten reactants by distillationand the polymer is isolated as a molten residue. A specifically usefulmelt process for making polycarbonates uses a diaryl carbonate esterhaving electron-withdrawing substituents on the aryls. Examples ofspecifically useful diaryl carbonate esters with electron withdrawingsubstituents include bis(4-nitrophenyl)carbonate,bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methylsalicyl)carbonate, bis(4-methylcarboxylphenyl)carbonate,bis(2-acetylphenyl) carboxylate, bis(4-acetylphenyl) carboxylate, or acombination comprising at least one of the foregoing esters. Inaddition, useful transesterification catalysts can include phasetransfer catalysts of formula (R³)₄Q⁺X, wherein each R³, Q, and X are asdefined above. Exemplary transesterification catalysts includetetrabutylammonium hydroxide, methyltributylammonium hydroxide,tetrabutylammonium acetate, tetrabutylphosphonium hydroxide,tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, or acombination comprising at least one of the foregoing.

The polyester-polycarbonates in particular can also be prepared byinterfacial polymerization as described above with respect topolycarbonates generally. Rather than utilizing the dicarboxylic acid ordiol per se, the reactive derivatives of the acid or diol, such as thecorresponding acid halides, in particular the acid dichlorides and theacid dibromides can be used. Thus, for example instead of usingisophthalic acid, terephthalic acid, or a combination comprising atleast one of the foregoing acids, isophthaloyl dichloride, terephthaloyldichloride, or a combination comprising at least one of the foregoingdichlorides can be used.

The polycarbonates can have an intrinsic viscosity, as determined inchloroform at 25° C., of 0.3 to 1.5 deciliters per gram (dl/gm),specifically 0.45 to 1.0 dl/gm. The polycarbonates can have a weightaverage molecular weight of 10,000 to 200,000 Daltons, specifically20,000 to 100,000 Daltons, as measured by gel permeation chromatography(GPC), using a crosslinked styrene-divinylbenzene column and calibratedto polycarbonate references. GPC samples are prepared at a concentrationof 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute.Combinations of polycarbonates of different flow properties can be usedto achieve the overall desired flow property. In an embodimentpolycarbonates are based on bisphenol A, in which each of A³ and A⁴ isp-phenylene and Y² is isopropylidene. The weight average molecularweight of the polycarbonate can be 5,000 to 100,000 Daltons, or, morespecifically 10,000 to 65,000 Daltons, or, even more specifically,15,000 to 35,000 Daltons as determined by GPC as described above.

The polyester-polycarbonates in particular are generally of highmolecular weight and have an intrinsic viscosity, as determined inchloroform at 25° C. of 0.3 to 1.5 dl/gm, and preferably from 0.45 to1.0 dl/gm. These polyester-polycarbonates may be branched or unbranchedand generally will have a weight average molecular weight of from 10,000to 200,000, preferably from 20,000 to 100,000 as measured by GPC asdescribed above.

The poly(carbonate-siloxane)s can have a weight average molecular weightof 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltons asmeasured by gel permeation chromatography using a crosslinkedstyrene-divinyl benzene column, at a sample concentration of 1 milligramper milliliter, and as calibrated with polycarbonate standards. Thepoly(carbonate-siloxane)can have a melt volume flow rate, measured at300° C./1.2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min),specifically 2 to 30 cc/10 min. Mixtures ofpolyorganosiloxane-polycarbonates of different flow properties can beused to achieve the overall desired flow property.

The foregoing polycarbonates can be used alone or in combination, forexample a combination of a homopolycarbonate and one or morepoly(carbonate-ester)s, or a combination of two or morepoly(carbonate-ester)s. Blends of different polycarbonate-esters may beused in these compositions.

In an embodiment, the polycarbonate film forming compositions (and thusthe films) contain less than 5 wt. % of fluorine, specifically less than4 wt. %, less than 3 wt. %, less than 2 wt. %, less than 1 wt. %, eachbased on the total weight of the composition.

In another embodiment, the polycarbonate film-forming compositions andfilms contain less than 1000 ppm, specifically less than 750 ppm, lessthan 500 ppm, or less than 50 ppm by weight of a fluorine-containingcompound. In a further embodiment, no fluorine-containing compound ispresent in the film-forming composition. Such compounds include, withoutlimitation, certain mold release agents, fillers (e.g., particulatePTFE), or flame retardants.

In another embodiment, the polycarbonate film-forming compositions (andthus the films) contain less than 1000 ppm, specifically less than 750ppm, less than 500 ppm, or less than 50 ppm by weight of a siliconecompound. In an embodiment, no silicone compound is present in thefilm-forming composition or film. Such silicone compounds include,without limitation, silicone oils, and polydimethyl siloxanes.

In an embodiment, the polycarbonate film-forming compositions and filmscontain less than 1000 ppm, specifically less than 750 ppm, less than500 ppm, or less than 50 ppm by weight of both a fluorine-containingcompound and a silicone compound. In an embodiment, nofluorine-containing compound and no silicone compound is present in thefilm-forming compositions or films.

Good electrical properties are obtained when the polycarbonatefilm-forming compositions and films contain low levels of certain metalions. Thus, the film-forming compositions and films contain less than 50ppm, specifically less than 40 ppm, 30 ppm, or 20 ppm by weight of eachof aluminum, calcium, magnesium, iron, nickel, potassium, manganese,molybdenum, sodium, titanium, and zinc.

In some embodiments it is desired to use polycarbonate film-formingcompositions and films that are essentially free of bromine andchlorine. “Essentially free” of bromine and chlorine means that thecomposition has less than 3 wt. % of bromine and chlorine, and in otherembodiments, less than 1 wt. % bromine and chlorine by weight of thefilm-forming composition. In other embodiments, the composition ishalogen free. “Halogen free” is defined as having a halogen content(total amount of fluorine, bromine, chlorine and iodine) of less than orequal to 1000 parts by weight of halogen per million parts by weight ofthe total composition (ppm). The amount of halogen can be determined byordinary chemical analysis such as atomic absorption.

The polycarbonate film-forming compositions can optionally furthercomprise one or more particulate fillers to adjust the propertiesthereof, for example dielectric constant, coefficient of thermalexpansion, and the like. Exemplary particulate fillers include silicapowder, such as fused silica and crystalline silica; boron-nitridepowder and boron-silicate powders; alumina, and magnesium oxide (ormagnesia); silicate spheres; flue dust; cenospheres; aluminosilicate(armospheres); natural silica sand; quartz; quartzite; titanium oxide,barium titanate, barium strontium, tantalum pentoxide, tripoli;diatomaceous earth; synthetic silica; and combinations thereof. All ofthe above fillers can be surface treated with silanes to improveadhesion and dispersion with the polymeric matrix resin. When present,the amount of particulate filler in the polycarbonate film-formingcompositions can vary widely, and is that amount effective to providethe desired physical properties. In some instances the particulatefiller is present in an amount from 0.1 to 50 vol. %, 0.1 to 40 vol. %,alternatively 5 to 30 vol. %, more particularly 5 to 20 vol. %, eachbased on the total weight of the film-forming composition.

The polycarbonate film-forming compositions can include variousadditives incorporated into dielectric substrate polymer compositionswith the proviso that the additives are selected so as to notsignificantly adversely affect the desired properties of thecompositions. In an embodiment, any additives are present in an amountthat provides less than 1,000 ppm of a compound having a molecularweight of less than 250 Daltons. Exemplary additives includeantioxidants, thermal stabilizers, light stabilizers, ultraviolet light(UV) absorbing additives, quenchers, plasticizers, lubricants,antistatic agents, flame retardants, anti-drip agents, and radiationstabilizers. Combinations of additives can be used. The foregoingadditives (except any fillers) are generally present individually in anamount from 0.005 to 20 wt. %, specifically 0.01 to 10 wt. %, based onthe total weight of the film-forming composition.

Suitable antioxidants can be compounds such as phosphites, phosphonitesand hindered phenols or mixtures thereof. Phosphorus-containingstabilizers including triaryl phosphites and aryl phosphonates areuseful additives. Difunctional phosphorus containing compounds can alsobe unseeded. Preferred stabilizers can have a molecular weight greaterthan or equal to 300. Some exemplary compounds aretris-di-tert-butylphenyl phosphite available from Ciba Chemical Co. asIRGAPHOS 168 and bis(2,4-dicumylphenyl) pentaerythritol diphosphiteavailable commercially from Dover Chemical Co. as DOVERPHOS S-9228.

Examples of phosphites and phosphonites include: triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxy pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol tri-phosphite, tetrakis(2,4-di-tert-butyl-phenyl)4,4′-biphenylene diphosphonite,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphiteand5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

Combinations comprising more than one organophosphorous compound arecontemplated. When used in combination the organophosphorous compoundscan be of the same type or different types. For example, a combinationcan comprise two phosphites or a combination can comprise a phosphiteand a phosphonite. In some embodiments, phosphorus-containingstabilizers with a molecular weight greater than or equal to 300 areuseful. Phosphorus-containing stabilizers, for example an aryl phosphiteare usually present in the composition in an amount from 0.005 to 3 wt.%, specifically 0.01 to 1.0 wt. %, based on total weight of thecomposition.

Hindered phenols can also be used as antioxidants, for example alkylatedmonophenols, and alkylated bisphenols or poly phenols. Exemplaryalkylated monophenols include 2,6-di-tert-butyl-4-methylphenol;2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol;2,6-dicyclopentyl-4-methylphenol;2-(alpha-methylcyclohexyl)-4,6-dimethylphenol;2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;2,6-di-tert-butyl-4-methoxymethylphenol; nonyl phenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol;2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol;2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol;2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.Exemplary alkylidene bisphenols include2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(alpha-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(alpha-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(alpha, alpha-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis-(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane andmixtures thereof.

The hindered phenol compound can have a molecular weight of greater thanor equal to 300 g/mole. The high molecular weight can help retain thehindered phenol moiety in the polymer melt at high processingtemperatures, for example greater than or equal to 300° C. Hinderedphenol stabilizers, are usually present in the composition in an amountfrom 0.005 to 2 wt. %, specifically 0.01 to 1.0 wt. %, based on totalweight of the composition.

In some embodiments, the polycarbonate film-forming compositions canfurther optionally include at least one additional amorphous polymer,again with the proviso that the polymers are selected so as to notprovide more than 5 wt. % of fluorine or silicon, or otherwise notsignificantly adversely affect the desired properties of thecompositions. Examples of such additional polymers include and are notlimited to poly(phenylene sulfone)s, poly(sulfone)s, poly(ethersulfone)s, poly(arylene sulfone), poly(phenylene ether)s,poly(etherimide)s, and poly(etherimide sulfone)s as well as blends andco-polymers thereof. When present, the polymer is used in an amount frommore than 0 to 12 wt. %, specifically 0.1 to 10 wt. %, more specificallyfrom 0.5 to 5 wt. %, all based on the total weight of the composition.In an embodiment, no polymer other than the polycarbonate is present inthe film-forming composition.

The polycarbonate film-forming compositions can be prepared by blendingthe ingredients under conditions for the formation of an intimate blend.Such conditions often include melt mixing in single or twin screw typeextruders, mixing bowl, or similar mixing devices that can apply a shearto the components. Twin-screw extruders are often preferred due to theirmore intensive mixing capability and self-wiping capability, over singlescrew extruders. It is often advantageous to apply a vacuum to the blendthrough at least one vent port in the extruder to remove volatileimpurities in the composition. Often it is advantageous to dry thepolycarbonate (and/or other additives) prior to melting. The meltprocessing is often done at 240° C. to 360° C. to avoid excessivepolymer degradation while still allowing sufficient melting to get anintimate polymer mixture free of any unmelted components. The polymerblend can also be melt filtered using a 40 to 100 micrometer candle orscreen filter to remove undesirable black specks or other heterogeneouscontaminants, for example any particles having a diameter of greaterthan 1 micrometer.

In an exemplary process, the various components are placed into anextrusion compounder to produce a continuous strand that is cooled andthen chopped into pellets. In another procedure, the components aremixed by dry blending, and then fluxed on a mill and comminuted, orextruded and chopped. The composition and any optional components canalso be mixed and directly extruded to form a film. In an embodiment,all of the components are freed from as much water as possible. Inaddition, compounding is carried out to ensure that the residence timein the machine is short; the temperature is carefully controlled; thefriction heat is utilized; and an intimate blend between the componentsis obtained.

The composition can be extruded using extruders conventionally used forthermoplastic compositions using a flat die. The extrusion cast filmmethod involves the melting of the polymer in an extruder, conveying ofthe molten polymer through a flat die of small lip gap separation, thestretching of the film at relatively high take-up speeds, and thecooling/solidification of the polymer to form the final film. Theextruder may be of the single- or twin-screw design, and a melt pump mayalso be used to provide a constant, non-pulsating flow of polymerthrough the die. The die lip gap may be as small as 100 to 200 micron,and the take-up rollers may operate at speeds of up to 200 m/min. Thedesign may also include the addition of a heated roll to temper/annealthe film and thus minimize the occurrence of frozen-in internalstresses. The edges of the film are often trimmed, and the film wound upon a roll using a tension-controlled winding mechanism. In someinstances, commercial and/or experimentally functionalized fillers canbe uniformly dispersed in the polymer prior to stretching the compositematerial into a thin film. In these cases, the compounding of the fillerinto the polymeric matrix to obtain a uniform dispersion can be done ona separate extruder or alternatively, and more preferably, on the sameextruder used to effect the melting of the polymer prior to thestretching operation. The accuracy of delivering a constant and uniformflow of molten polymer through the die, the rheological properties ofthe polymer used to make the film, the cleanliness of both resin andequipment, and the mechanical characteristics of the take-up mechanismwill all contribute to the successful preparation of these extrudedfilms having relatively small thicknesses.

In an embodiment, the extrusion cast film method is one-step, scalableto larger size equipment, and does not require the use of any solvent.Even for the case of polymers of high molecular weight and/or high glasstransition temperature; this extrusion process can be properly designedto provide an environment for the polymer that does not lead toexcessive temperatures that can cause the thermal or mechanicaldegradation of the material. The use of a filtration device for the meltproduces a film that is virtually free of contaminants, such as gels andblack specks, which would damage the dielectric performance of thesefilms if not properly removed from the melt. The films produced by thismethod are thin (10 micron in thickness, and even thinner), of uniformthickness across the web, flat with almost no wrinkles or surfacewaviness, and relatively free of contamination.

The melted composition can be conveyed through the extruder die using amelt pump. In an embodiment, the film is extruded at temperatures from250° C. to 500° C., for example 300° C. to 450° C., and the extrudedfilm is uniaxially stretched to produce the dielectric substrate film.Specifically, the components of the film-forming composition arecombined, melted, and intimately mixed, then filtered to removeparticles greater than 1 micrometer; extruded through a flat die at theforegoing temperatures; and then uniaxially stretched. After stretching,the film can be directly metallized as described below, or wound on atake-up roll for storage or shipping. The film can have a length of atleast 10, or 100 to 10,000 meter, and a width of at least 300, or 300 to3,000 millimeter. The rate which the film can be extruded can vary. Incommercial embodiments, the rate at which the film can be extrudedvaries from 10 lb/hr (4.5 kg/hr) to 1000 lb/hr (450 kg/hr). The rate atwhich the film can be pulled from the die plate of the extruder (thetake-up speed) can range from 10 meter/minute to 300 meter/minute.

The films can be metallized on at least one side thereof. A variety ofmetals can be used depending on the intended use of the film, forexample copper, aluminum, silver, gold, nickel, zinc, titanium,chromium, vanadium, and others. The films are metallized at least on thesmooth side, that is, the side having an average surface roughness Ra ofless than +/−3% of the average film thickness as determined by opticalprofilometry. Methods for the metallization of polymer films are known,and include, for example, vacuum metal vapor deposition, metalsputtering, plasma treatments, electron beam treatments, chemicaloxidation or reduction reactions, as well as electroless wet-chemicaldeposition. The films can be metallized on both sides by conventionalelectroless plating. In another embodiment, a patterned metal layer canbe formed on a surface of the film, for example by ink jet printing. Thethickness of the metallized layer is determined by the intended use ofthe metallized film, and can be, for example, 1 Angstrom to 1000nanometers, 500 nanometer, or 10 nanometer. In an embodiment, thethickness of the metal film can be 1 to 3000 Angstrom, 1 to 2000Angstrom, or 1 to 1000 Angstrom. If a conductive metal is used, theresistivity of the metal layer on the polymer film can vary from 0.1 to1000 Ohm per square or 0.1 to 100 Ohm per square.

The surface of the film to be metallized can be pre-treated, for exampleby washing, flame treatment, plasma discharge corona discharge, or thelike, for example to enhance adhesion of the metal layer. One or moreadditional layers can be deposited on the metal layer, for example aclear coat (such as a poly(methyl methacrylate) or poly(ethylmethacrylate) to provide scratch resistance), or another layer of thepolycarbonate film to form a laminate.

The films and metallized films thus produced have a variety ofadvantageous physical properties. The films have at least one regionthat is wrinkle-free, that is, sufficiently flat and smooth so that whena surface thereof is metallized, the metallized film has anadvantageously consistent surface morphology. In an embodiment, thebreakdown strength of the un-metallized film is at least 300Volt/micrometer, alternatively at least 350 Volt/micrometer,alternatively at least 400 Volt/micrometer. In an embodiment, thebreakdown strength of the unmetallized film can be up to 520, 550, 580,610, 640, 670, and 700 Volt/micrometer.

The flatness of the wrinkle-free regions of the films can be determinedby measuring the variation in thickness of the film over a specificarea. Here, flat films have variation of the thickness of the film ofplus or minus (+/−) 10% or less, alternatively +/−9% or less, +/−8% orless, +/−6% or less, or +/−5%, +/−4%, +/−3%, +/−2%, +/−1% or less, basedon the average thickness of the film over the measured area. In anembodiment, the variation in thickness can be as low as +/−1%.

The smoothness of the wrinkle-free regions of a surface of the films canbe quantitated by measuring the surface roughness average (“Ra”) of thesurface by optical profilometery. Here, the wrinkle-free regions of thefilms have a surface having an Ra of less than +/−3%, less than /−2%, ora low as +/−1% of the average thickness of the film as measured byoptical profilometery.

In a particularly advantageous feature, the wrinkle-free regions can beproduced over a large area of the film. For example, at least 80%, atleast 85%, at least 90%, at least 95%, or at least 97% of area of thefilm can be wrinkle-free. As such, the films can have wrinkle-freeregions having a lower limit and/or an upper limit. The range caninclude or exclude the lower limit and/or the upper limit. The lowerlimit and/or upper limit can be selected from 80, 81, 82, 83, 84, 85,86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100% of thearea of the film. In another embodiment, the wrinkle-free region canhave a contiguous area of at least 1 square meter (m²), at least 2 m²,at least 3 m², at least 5 m², at least 10 m², at least 20 m², at least50 m², or at least 100 m². The large size of the wrinkle-free regionsoffers a significant manufacturing advantage, in that the metallizedfilms can be manufactured, stored, and shipped in roll form. Thus, thefilm can have a length of at least 10 meter, and a width of at least 300millimeter, wherein at least 80%, at least 85%, at least 90%, at least95%, or at least 97% of area of the film is the wrinkle-free region. Inanother embodiment, the film has a length of 100 to 10,000 meter, and awidth of 300 to 3,000 millimeter, wherein at least 80%, at least 85%, atleast 90%, at least 95%, or at least 97% of area of the film is thewrinkle-free region. As such, when the films have a length ranging from100 to 10,000 meters, the films can have wrinkle-free regions having alower limit and/or an upper limit. The range can include or exclude thelower limit and/or the upper limit. The lower limit and/or upper limitcan be selected from 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92,93, 94, 95, 96, 97, 98, 99, and 100% of the area of the film.

The composition and manufacturing method can be varied to achieve thedesired performance properties, in particular electrical properties.

The films can have a high dielectric constant, in particular greaterthan 2.7, greater than 3.0, or greater than 3.2, 3.3, 3.4, 4.2, 4.3,4.4, or 4.5, up to 7.0.

The films further can have a dielectric constant that is stable up tothe Tg of the polymer that they are made from. Generally, the films areused in environment at a temperature that is lower than the film'spolymer's respective Tg, e.g. approximately 20° C. lower. In oneembodiment, films further can have a dielectric constant that is stableup to 50° C., up to 60° C., up to 70° C., up to 80° C., up to 90° C., upto 100° C., up to 110° C., up to 120° C. or higher.

The films and the metallized films can be essentially solvent-free, thatis, contain less than 1,000 ppm, less than 750 ppm, less than 500 ppm,or less than 250 ppm of a compound having a molecular weight of lessthan 250 Daltons.

The films and the metallized films can have less than 50 ppm, less than25 ppm, or less than 10 ppm each of aluminum, calcium, magnesium, iron,nickel, potassium, manganese, molybdenum, sodium, titanium, and zinc inthe polycarbonate layer.

The films and the metallized films can have less than 1000 ppm, lessthan 500 ppm, less than 250 ppm, or less than 100 ppm each of afluorine-containing compound or a silicone-containing compound.

The films and the metallized films can have no observable specks or gelsover an area of at least 3 square meters, or over an area of at least 9square meters when viewed at a distance of 0.3 meter withoutmagnification.

The films and the metallized films can have no observable voids over anarea of at least 3 square meters, or over an area of at least 9 squaremeters when viewed at a magnification of 50×.

The metallized films can have a dissipation factor, as measured bydielectric spectroscopy, ranging from more than 0 and less than 5%,alternatively more than 0 and less than 4%, alternatively more than 0and less than 3%, alternatively more than 0 and less than 2%,alternatively more than 0 and less than 1%. In one embodiment, the filmshave a low dissipation factor, that is, less than 0.1%, or less than0.08%.

The polycarbonate films can be used in any amorphous film application,but are particularly suitable for metallization. The metallized filmscan be used in any metallized film application, but are particularlysuitable for electrical applications, for example as capacitors orcircuit materials. High energy density, high voltage non-polarcapacitors can be made using a metalized polymer film that is wound intoa cylindrical shape. In a specific embodiment, the polycarbonate film isextruded, then metallized by spraying a conductive metal such as copperor aluminum onto the moving polymer film via vapor deposition in avacuum chamber, to a thickness from 1 Angstrom to 1000 nanometers, 1 to3000 Angstrom, or 1 to 1000 Angstrom. The resistivity of the metal onthe polymer film can be in a range from about 0.1 Ohm per square to 100Ohm per square. Before the metallization process is performed, thepolymer film can be appropriately masked to provide unmetallized marginsat the edges of the width of the film, so that alternate layers ofmetallized film (when the capacitor is assembled) have unmetallizedregions at opposite edges to prevent electrical shorting of theelectrodes of the capacitor when the end metallization is ultimatelyapplied.

The capacitors can then be fabricated by rolling two stacked metalizedpolymer films into a tubular shape. Electrical wires are connected toeach metal layer. In a specific embodiment, two separate rolls of themetallized film are placed in a capacitor winder and wound tightlytogether on a mandrel (which may subsequently be removed) so that thelayers are arranged in the sequence polycarbonate/metallizedlayer/polycarbonate/metallized layer, to replicate a typicalconstruction of a capacitor, i.e., a dielectric with two metallic layerson opposite sides. The two rolls of film are wound with the unmetallizedmargins on opposite sides.

The extent of winding of the capacitor depends on the physical size ofthe capacitor desired or on the capacitance desired. Tight winding ofthe two rolls aids in removing any entrapped air that might otherwisecause premature breakdown. Individual capacitors can be processed in aclean room environment of at least class 100, incorporating HEPAfilters, to reduce the likelihood of contamination of the contact pointbetween the dielectric film layers by foreign particles, as well asreducing moisture intake in the dielectric. Electric winding can be usedto better maintain uniform tension on each capacitor. The capacitor canthen be taped at the edges thereof and strapped in a tray open on bothsides, to prevent unwinding of the film layers and to allow the edges orends of the cylinder to be sprayed with a conductive element, forexample with a high zinc content solder followed by a regular softer endspray solder of 90% tin, 10% zinc. The first spray scratches themetallized surface and creates a trough to achieve better contact withthe metallization on the dielectric film. The combination of end spraysfurther aids better contact adhesion with the final termination.Subsequently, conductive, e.g., aluminum leads can then be soldered ontoeach end to form the final termination. One termination can be spotwelded to the bottom of the can, while the other termination can beparallel welded to the lid. The capacitor may be filled with a liquidimpregnate (for example, isopropyl phenyl sulfone), in vacuum fillingapparatus, and closed.

Other capacitor configurations are possible. For example, the capacitorcan have a flat configuration comprising at least a first and a secondelectrode disposed in a stacked configuration; and the polycarbonatefilm disposed between and in at least partial contact with each of thefirst and second electrodes. Additional polycarbonate films andelectrode layers can be present in alternating layers. Thus, amultilayer article for forming an electronic device is within the scopeof the present claims, comprising a polycarbonate layer/metallayer/dielectric layer, wherein the dielectric layer can be apolycarbonate film as describe herein, or other dielectric material.Additional layers (e.g., additional alternating dielectric/metal layers)can optionally be present.

The following Examples are illustrative, and non-limiting.

EXAMPLES Materials

The Examples were performed according to the procedures below using thematerials identified in Table 1.

Testing Procedures

Film thickness is measured using a Filmetrics F20 Thin Film MeasurementSystem, manufactured by Filmetrics Inc., San Diego, Calif., whichemploys spectral reflectance to measure a film's thickness by reflectinglight off the film and analyzing the reflected light over a range ofwavelengths.

Surface roughness is determined using an optical profilometermanufactured by Wyko NT100, operated in the unit's standard operatingmode. Measured values are reported under conventional headings such asRa, Sq, etc., in which “R” indicates that the value was calculated using2D data and represents linear or profile roughness and “S” indicatesthat the value was calculated using 3D data and represents surface orarea roughness. The second character indicates the formula type used inthe calculation, where for example “a” indicates an arithmetic formulaand “q” indicates a root mean square formula.

Metal contamination was determined by ICP (Inductively Coupled PlasmaSpectroscopy, which is a known method for measuring metalcontamination).

Dielectric Constant (DK) and Dissipation Factor (DF) were determinedusing dielectric spectroscopy. Polymer films with very uniform filmthickness are used as the test samples. The film thickness d isprecisely determined by micrometers or optical thickness gauges (if thefilm is transparent). Gold or aluminum electrodes with known area A aredeposited on both sides of the film sample using sputtering or thermalevaporation. The metallized sample is then loaded into atemperature-controlled chamber and electrically connected with adielectric spectrum analyzer, such as the Novocontrol BroadbandDielectric Spectrometers. The spectrum analyzer measures the capacitanceC and the dissipation factor DF. The DK of the sample is calculatedbased on the measured capacitance and the area and thickness of thesample:

${{DK} = \frac{Cd}{A\; ɛ_{0}}},$

where ∈₀=8.85×10⁻¹² F/m, the vacuum permittivity constant.

Dielectric breakdown was determined in accordance with ASTM D-149. Apiece of polymer film with uniform thickness is used as the test sampleand the thickness is measured using the same method as for the DK and DFmeasurement. The film sample is tested as a bare film without electrodesdeposited on its surface. The film sample is placed between two metalelectrodes, where the bottom electrode is a flat copper plate and thetop electrode is a stainless steel ball with ¼ inch diameter. During thebreakdown measurement, a continuously increasing DC voltage is appliedon the sample between the two electrodes, starting from 0 V andincreasing with a fixed rate of 500 V/sec. The DC voltage is appliedusing a high voltage power supply, such as the Hipotronics DC PowerSupply. The voltage increases until dielectric breakdown occurs, whichgenerates large current and causes the power supply to automaticallyreset through its protection circuits. The highest reached voltage isrecorded as the breakdown voltage V_(BD), and the breakdown electricfield E_(BD) is determined by dividing V_(BD) by the film thickness d.This method was employed unless another method is identified.

Insulation resistance is measured by a megohm meter with a time testedfunction, temperature meter, and similar features.

Compression Molding Procedure—Approximately 1.5 grams of powder orpellets were weighed into a 20 ml vial and covered with a Kim wipe andrubber band. This was dried in a vacuum oven overnight at 80° C. Thenext day the vacuum was removed and nitrogen if used to fill the vacuumoven. Samples were removed quickly and the vial was capped. Theresulting dry, capped samples were held for at least 4-8 hours. A 4×5inch (101 mm×127 mm) ferro-plate was placed on a larger steel plate.Three shims that are 2 inches (101 mm) long and of the desired samplethickness were placed on the ferro-plate in such a manner to form 3sides of a square. When ready to mold, individual samples were quicklypoured into the center, and another ferro-plate and steel plate wasplaced on top. This entire stack was placed into an automated press suchas a Tetrahedron press. The initial temperature setting was 512° F.(270° C.) and the platen was raised just enough to lift the upperplaten, but not enough to engage the hydraulics. After 3 minutes ofequilibration, the platen was raised to engage the automated press andthe pressure rapidly rose to 15,000 lbs (6,804 kg) and was held therefor 5 minutes at this temperature and pressure. The press thenautomatically cooled to 212° F. (100° C.) while maintaining the 15,000lbs (6,804 kg) of pressure and held at the final temperature for 5minutes. Once the press released at the end, the sample was quicklyremoved and the plates were pulled away from the sample while stillwarm. If a sample remained stuck to the plates, they were soaked inwater for a period of time to allow easy release.

This procedure was used for materials with Tg's of approximately 180° C.For polycarbonates that have Tg's in the 145° C.-150° C. range, theinitial and final temperatures of the press were each reduced by 20° C.It was observed that hazy films were produced if the final temperatureswere in the 200° C.-220° C., apparently from crystallization in themelt. Film thicknesses typically ranged from 225-275 μm depending on theTg of material. If low bulk density powders produced bubbles followingthis procedure, the samples were cold pressed first. The 1.5 grams ofpowder was placed in a 1 inch (25.4 mm) diameter mold and Carver pressedto form a coin-like disk. This could then be dried overnight in the samemanner and used to make films. Finally, film thicknesses could beadjusted by using different thickness shims

TABLE 1 Material Trade Name Source Polycarbonate 1 (PC1) Lexan 135 ResinSABIC Innovative Plastics Polycarbonate 2 (PC2) APEC Bayer PMR-00039808Resin Polycarbonate 3 (PC3) Lexan XHT 4141 SABIC Innovative PlasticsResin Polycarbonate 4 (PC4) Lexan 151 Resin SABIC Innovative PlasticsPolycarbonate 5 (PC5) Lexan ML5221 SABIC Innovative Plastics ResinPolyetherimide (PEI) Ultem 1000 Resin SABIC Innovative PlasticsCopolyestercarbonate 1 Lexan Resin SABIC Innovative Plastics (CPC1)Copolyestercarbonate 2 Lexan Resin SABIC Innovative Plastics (CPC2)Copolyestercarbonate 3 Lexan Resin SABIC Innovative Plastics (CPC3)Copolyestercarbonate 4 Lexan Resin SABIC Innovative Plastics (CPC4)Copolyestercarbonate 5 Lexan Resin SABIC Innovative Plastics (CPC5)Copolyestercarbonate 6 Lexan Resin SABIC Innovative Plastics (CPC6)

Comparative Example 1

Two polycarbonate resins of different glass transition temperatures, PC1(a bisphenol A-based polycarbonate) and PC2, were extruded into thinfilms, and their dielectric breakdown strengths evaluated. The resultsare presented in Table 2.

TABLE 2 Comp. Ex. 1A Comp. Ex. 1B Comp. Ex. 1C Comp. Ex. 1D Die size(in/mm)   3/76.2   3/76.2   3/76.2   3/76.2 Die gap (in/micron)0.005/125   0.005/125   0.005/125   0.005/125   Screw design Standard,Low Standard, Low Standard, Low Standard, Low Mixing mixing mixingmixing Material PC1 PC1 PC2 PC2 Melt Temperature (° C.) 311 ExtruderBarrel Temperature Set Actual Set Actual Set Actual Set Actual Die headT (° C.) 320 316 340 340 Die adaptor T (° C.) 320 316 340 340 Adaptor T(° C.) 320 320 340 340 Extruder Front T (° C.) 310 310 340 340 ExtruderMiddle T (° C.) 300 301 340 340 Extruder Middle T (° C.) 280 280 340 340Extruder Back T (° C.) 260 259 320 320 Screw speed (rpm) 200 200 200Torque (%/Nm)   43/11.2  35/9.4  30/8.6  30/8.6 Die pressure (psi)/(MPa) 745/5.13  560/3.86  600/4.13  420/2.89 Throughput (set) (lb/hr)/(kg/hr) 0.5/0.227  0.25/0.114  0.5/0.227  0.25/0.114 Throughput (actual)0.4822/0.219  0.2441/0.111  0.4822/0.219  0.2441/0.111  (lb/hr)/(kg/hr)Roll speed actual 11.4/3.47 11.4/3.47 11.4/3.47 11.4/3.47(ft/min)/(m/min) Forced air to cool film @ die Yes Yes Yes Yes exit Filmthickness (micron) 8.9/0.5/20 4.9/0.6/20 10.3/1.4/20 5.4/0.7/20 Mean Stdev/#samples Breakdown strength (V/micron) 804/99/20 818/93/20838/121/20 787/151/20 Mean/St dev/#samples

Discussion: Table 2 shows that films of PC1 (Tg=152° C.) and PC2(Tg=204° C.) of less than 7 micron in thickness and dielectric breakdownstrengths higher than about 750 V/micron can be made by melt extrusion.These films were made at polymer rates equal to 0.25 lb/hr, and take-upspeed equal to 11.4 ft/min. Since these films showed wrinkles, die linesand other imperfections, they did not have the level of quality that isrequired for the manufacture of electrostatic film capacitors.

Comparative Example 2

Table 3 shows the film thicknesses and dielectric breakdown strengths offilms made by extrusion from PC3 having a glass transition temperatureequal to 181.5° C.

TABLE 3 Comp. Ex. 2A Comp. Ex. 2B Comp. Ex. 2C Comp. Ex. 2D Comp. Ex. 2EMaterial PC3 PC3 PC3 PC3 PC3 Die size (in)/(mm)   3/76.2   3/76.2  3/76.2   3/76.2   3/76.2 Die gap (in/micron) 0.005/125   0.005/125  0.005/125   0.005/125   0.005/125   Screw design Standard, Standard, LowStandard, Low Standard, Low Standard, Low Low mixing mixing mixingmixing mixing Melt Temperature (° C.) ~315 Extruder Barrel TemperatureSet Actual Set Actual Set Actual Set Actual Set Actual Die head T (° C.)320 315 320 330 Die adapter T (° C.) 320 320 330 Adapter T (° C.) 320320 320 Extruder Front T (° C.) 320 320 320 Extruder Middle T (° C.) 320320 320 Extruder Middle T (° C.) 300 300 300 Extruder Back T (° C.) 280280 280 Screw speed (rpm) 250 250 250 250 250 Torque (%/Nm)  37/10.4  37/10.2  30/8.2  25/7.8 Die pressure ~820/5.65    810/5.58  750/5.17 675/4.65  500/3.45 (psi)/(MPa) Throughput (set)  0.5/0.227  0.5/0.227 0.5/0.227  0.4/0.182  0.4/0.182 (lb/hr)/(kg/hr) Roll speed actual7.6/2.32 11.4/3.47 15.2/4.63 15.2/4.63 17.1/5.21 (ft/min)/(m/min) Filmwidth (in)/(mm) About About 2.5/63.5  2.5/63.5 Forced air to cool filmYes/8 psi Yes Yes Yes Yes @ die exit Film thickness (micron) 13.7/1.2/2010.7/1.6/20 7.5/1.3/20 6.0/1.1/20 4.4/0.8/20 Mean/St dev/#samplesBreakdown strength 698/93/20 710/119/20 629/131/20 713/136/20 706/121/20(V/micron) Mean/St dev/#samples

Discussion: Although these films had a relatively high breakdownstrength, the presence of wrinkles, die lines and other imperfectionsmade them unsuitable for the manufacture of electrostatic filmcapacitors.

Example 1

Table 4 shows the thickness distribution across the web of a film of PC4about 6 micrometers thick, about 45 in wide and about 6,000 ft long.

TABLE 4 Distance from left Film Thickness edge Measurement # (μm)(in)/(mm)  1 7.4171  2/51  2 6.1876  4/102  3 6.5986  6/152  4 5.6736 8/203  5 6.3265 10/254  6 6.0949 12/305  7 6.0564 14/355  8 6.096116/406  9 5.4231 18/457 10 6.3784 20/508 11 5.4621 22/558 12 6.134324/610 13 5.2897 26/660 14 6.6928 28/711 15 6.0192 30/762 16 5.759132/813 17 5.6524 34/864 18 5.8041 36/914 19 5.4151 38/965 20 5.869540/1016 21 5.2719 42/1067 22 5.935 44/1118 AVERAGE 5.98 ST DEV 0.51 %Error 9

These results showed that 22 measurements of the film thickness acrossthe web gathered around the mean value of 5.98 micron with one standarddeviation of only 0.51 micron.

Table 5 shows the dielectric breakdown strength of the film of PC4 forwhich thickness measurements were recorded on Table 4.

TABLE 5 Breakdown Breakdown Thickness Voltage Strength Site (micron)(kVDC) (C/micron)  1 5.56 3.79 682  2 5.56 3.79 682  3 5.61 3.74 667  45.60 4.34 775  5 5.71 4.37 765  6 5.72 4.13 722  7 5.83 4.35 746  8 5.914.39 743  9 5.90 3.81 646 10 5.95 4.39 738 11 5.99 3.22 538 12 6.03 4.39728 13 6.05 4.54 750 14 6.08 4.86 799 15 6.22 4.64 746 16 6.24 3.93 63017 6.30 4.45 706 18 6.33 4.38 692 19 6.35 4.87 767 20 6.35 4.40 693 Mean6.0 4.24 711 StDev 0.28 0.41 60

Discussion: These results showed that the film of PC4 had a breakdownstrength in excess of 700 V/micron with a standard deviation of only 60V/micron and failed at an average voltage of about 4,240 VDC.

Table 6 shows the surface roughness (Ra) of the two sides of the samefilm of PC4 as measured by Optical Profilometry.

TABLE 6 Sample Ra (um) Rq (um) Side 1 0.0126 0.0161 0.0142 0.0185 0.01320.0169 0.0187 0.0238 0.0182 0.0229 0.0154 0.0191 average 0.0154 0.0196stdev 0.0026 0.0031 Side 2 0.0109 0.0140 0.0108 0.0149 0.0097 0.01250.0104 0.0138 0.0100 0.0127 0.0133 0.0171 average 0.0108 0.0142 stdev0.0013 0.0017

These results showed that the average roughness values were about 15 and11 nm for both sides, which were below the 180 nm allowed by thespecification for the manufacture of electrostatic metallized filmcapacitors (less than about 3% of the average film thickness).

Elemental analysis by Inductively Coupled Plasma Mass Spectroscopy wasperformed on several films of polycarbonate and polyetherimide made bythe extrusion method. Table 7 below shows that the amounts of metalsfound in these films were within the acceptable ranges allowed by thespecification for the manufacture of metallized film capacitors.

TABLE 7 ICP - Results in μg/g (ppm). Al, μg/g Ca, μg/g Mg, μg/g Ni, μg/gNa, μg/g Fe, μg/g Sample Name ±95% CI ±95% CI ±95% CI ±95% CI ±95% CI±95% CI PC5 5.7 ± 0.2 57 ± 0.3 2.1 ± 0.1 11.3 ± 0.5 2.4 ± 0.1 28.0 ±0.5  2.3 ± 0.1 204 ± 0.5  1.2 ± 0.1 10.5 ± 0.4 3.8 ± 0.1 22.9 ± 0.3  2.5± 0.1 198 ± 0.5  0.9 ± 0.1  9.3 ± 0.4 6.1 ± 0.1 33.8 ± 0.3  PEI8.5 2.9 ±0.2 81 ± 0.3 1.0 ± 0.1 35.1 ± 0.5 10.3 ± 0.1  108 ± 0.6 2.9 ± 0.1 88 ±0.3 0.8 ± 0.1 31.8 ± 0.5 12.0 ± 0.1  136 ± 0.7 PEI7.2 3.7 ± 0.2 57 ± 0.31.2 ± 0.1 29.2 ± 0.6 13.7 ± 0.1  142 ± 0.8 3.6 ± 0.2 47 ± 0.3 1.0 ± 0.136.1 ± 0.6 12.6 ± 0.1  141 ± 0.8 PC4 3.1 ± 0.1 33 ± 0.2 1.0 ± 0.1 23.9 ±0.3 2.0 ± 0.1 24 > X > 0.7 2.3 ± 0.1 32 ± 0.2 0.7 ± 0.1 18.2 ± 0.3 2.0 ±0.1 24 > X > 0.7 2.9 ± 0.1 40 ± 0.2 0.8 ± 0.1  9.1 ± 0.3 2.5 ± 0.1 24 >X > 0.7 Sample Ti, μg/g Cr*, μg/g Cu*, μg/g Zn, μg/g K, μg/g Mn, μg/gMo, μg/g Name ±95% CI ±95% CI ±95% CI ±95% CI ±95% CI ±95% CI ±95% CIPC5 1.2 ± 0.1 3.3 ± 0.3 3.3 ± 0.5 5.7 ± 0.3 1.7 ± 0.3 0.4 ± 0.1 1.1 >X > 0.3 0.4 ± 0.1 3.3 ± 0.3 2.7 ± 0.5 16.9 ± 0.3  3.3 ± 0.2 0.4 ± 0.11.1 > X > 0.3 0.5 ± 0.1 4.9 ± 0.3 3.5 ± 0.5 17.4 ± 0.3  5.4 ± 0.2 0.6 ±0.1 1.1 > X > 0.3 PEI8.5 0.4 ± 0.1 191 ± 0.5  2.2 > X > 1.0 9.5 ± 0.31.8 ± 0.3 2.5 ± 0.1 1.1 > X > 0.3 0.3 ± 0.1 257 ± 0.5  2.3 ± 0.5 11.5 ±0.3  2.2 ± 0.3 3.1 ± 0.1 1.1 ± 0.3 PEI7.2 .03 ± 0.1 206 ± 0.5  2.6 ± 0.57.8 ± 0.3 2.3 ± 0.3 3.3 ± 0.1 1.1 ± 0.3 0.3 ± 0.1 213 ± 0.5  2.6 ± 0.510.9 ± 0.3  1.7 ± 0.3 3.2 ± 0.1 1.2 ± 0.3 PC4 0.4 ± 0.1 1.6 ± 0.3 <1 5.6± 0.3 1.3 > X > 0.4 <0.2 1.1 > X > 0.3 0.3 ± 0.1 1.3 ± 0.1 <1 6.6 ± 0.31.3 > X > 0.4 <0.2 <0.3 0.4 ± 0.1 1.2 > X > 0.4 <1 7.1 ± 0.3 1.3 > X >0.4 <0.2 <0.3 PC5, made on lab PRISM extrusion line, 0.5 lb/hr, 5.4ft/min, ~25 micron PEI8.5, made on lab PRISM extrusion line, 0.4 lb/hr,9 ft/min, 8.5 micron, 475 V/micron PEI7.2, Ultem 1000, PRISM extrusionline, 0.3 lb/hr, 9 ft/min, 7.2 micron, 553 V/micron PC4, extruded 6micron film, 711 V/micron. *Cr and especially Cu could be partially lostafter ashing, thus their results are for information only.

Results indicate that some impurities are not uniformly distributed inthe samples. For the case of the PC4 polycarbonate film, which is thesame film described in Table 4 above, these results were consistent withthe relatively high values of dielectric breakdown strength measured inthis same film (Table 5 above).

Example 2

The film of PC4 described in Table 4 was metallized and wound intoelectrostatic film capacitors of about 13.5 microF. Two roll pairs ofextruded polycarbonate film were metalized with zinc heavy edge andaluminum web electrodes. The Rolls were marked in pairs as #3 & #4 and#2 & #5. The film in both roll pairs was 6 micron thick and 100 mm wide.A series of capacitors were automatically wound from each roll pair set.

Measurement of Breakdown Voltage:

Two capacitors from each roll pair set (units #1 and #5) were ramped in50 VDC steps, 90 seconds per step, until the unit short circuited asmonitored by Insulation Resistance using 500 megohm (or less) as thefailure (breakdown point). The results are reported on Tables 8 and 9.

TABLE 8 Breakdown Test Results Unit #1 Break-Down Break-Down S/N Test(VDC) Test (VDC)  1 900 850 Voltage Rolls #2 & #5 Rolls #3 & #4 VDC IR(MΩ) IR (MΩ)  50 6,250 6,250 100 11,111 11,111 150 10,714 9,375 20011,765 11,765 250 10,870 10,870 300 9,677 9,677 350 8,750 13,462 40011,111 11,111 450 9,783 10,000 500 8,065 8,065 550 6,250 7,237 600 4,6156,316 650 3,611 5,417 700 2,593 4,118 750 1,923 3,216 800 1,379 2,105850 988 2 900 30 n/a

TABLE 9 Breakdown Test Results Unit #5 Break-Down Break-Down S/N Test(VDC) Test (VDC)  5 850 900 Voltage Rolls #2 & #5 Rolls #3 & #4 VDC IR(MΩ) IR (MΩ)  50 16,666 16,666 100 16,666 14,285 150 21,428 16,666 20022,222 16,666 250 22,727 17,857 300 23,076 15,000 350 20,588 15,909 40020,000 15,384 450 15,517 11,842 500 11,627 10,204 550 9,322 7,857 6007,058 6,382 650 5,327 5,200 700 3,846 3,977 750 2,788 2,952 800 1,5502,156 850 220 1,534 900 n/a 78Tables 8 and 9 show that the breakdown voltage of these capacitors wasbetween 850 V and 900V.

Insulation Resistance with Voltage:

Typically, based on historical ratings, 6 micron thick PC film is ratedat 200 VDC with a DWV requirement of 400 VDC. Three other 13.5 microFcapacitors were tested for dielectric withstanding voltage (DWV) andmeasured for insulation resistance at 400 VDC DWV/200 VDC IR; 600 VDCDWV/300 VDC IR; and 800 VDC DWV/400 VDC IR to compare the extruded PCfilm performance to typical solvent cast PC results (Table 10).

TABLE 10 Breakdown Test Results Insulation Resistance vs Voltage. Rolls#2 & #5 Rolls #3 & #4 Unit Break-Down Break-Down S/N Test (VDC) Test(VDC) 1 900 850 Unit IR AT Rolls #2 & #5 Rolls #3 & #4 S/N (VDC) IR (MΩ)IR (MΩ) 2 200 66,700 66,700 3 300 13,600 10,700 4 400 1,000 400

Insulation Resistance with Temperature: Units #2, 3 and 4 from each ofthe two groups were measured for Insulation Resistance at +25° C., +85°C., +105° C. and +125° C., and three different voltages, 200 VDC, 300VDC and 400 VDC (Table 11A, 11B and 11C)

TABLE 11A Temperature Effects on IR (MΩ) at 200 VDC TemperatureTemperature Temperature Temperature Rolls (° C.) 25 (° C.) (° C.) (° C.)Section S/N4 25 85 105 125 Rolls #2 & #5 64,500 7,200 4,200 1,900 Rolls#3 & #4 69,000 9,600 6,700 4,900

TABLE 11B Temperature Effects on IR (MΩ) at 300 VDC TemperatureTemperature Temperature Temperature Rolls (° C.) 25 (° C.) (° C.) (° C.)Section S/N3 25 85 105 125 Rolls #2 & #5 77,000 4,800 3,100 1,700 Rolls#3 & #4 79,000 8,500 5,400 4,100

TABLE 11C Temperature Effects on IR (MΩ) at 400 VDC TemperatureTemperature Temperature Temperature Rolls (° C.) 25 (° C.) (° C.) (° C.)Section S/N2 25 85 105 125 Rolls #2 & #5 Shorted N/A N/A N/A Rolls #3 &#4 57,000 5,900 4,900 2,100

The purpose of the following Examples is to demonstrate the performanceof copolyestercarbonates. Six copolyestercarboantes, designated CPC1,CPC2, CPC3, CPC4, CPC5, and CPC6, were used in the following examples.Further details on the composition of these copolyestercarbonates areprovided in Table 1 above, in the following discussion and in Table 12,below.

CPC1 is a copolycarbonate of 67 mole % Bisphenol A and 33 mole %3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one.

CPC2 is a branched Bisphenol A polycarbonate with hydroxybenzonitrileendgroups.

CPC3 is a polyestercarbonate with about 19 mole % resorcinol, an iso andtere (1:1) phthalate ester linkages, 6 mole % resorcinol carbonatelinkages and about 75 mole % BPA carbonate linkages. Mw ˜30,000.

CPC4 is a copolycarbonate with about 80 mole % resorcinol iso and tere(1:1) phthalate ester linkages, 10 mole % resorcinol carbonate linkagesand about 10 mole % BPA carbonate linkages. Mw˜21,000

CPC5 is a BPA copolyester carbonate containing about 80 mole % of a 93:7mixture iso and tere phthalate ester groups and the remainder BPAcarbonate groups, Mw˜28,000.

CPC6 is a BPA copolyester carbonate containing about 60 mole % of a50:50 mixture iso and tere phthalate ester groups and the remainder BPAcarbonate groups.

TABLE 12 Copolyester- Isophthalic/Terephthalic carbonate % Ester ratioPhenol CPC 3 90 50/50 Resorcinol CPC 4 20 50/50 Resorcinol CPC 5 8093/7  Bisphenol A CPC 6 60 50/50 Bisphenol A

Samples of these materials were evaluated according to the testingprocedures summarized above, and the results are reported on Table 13.

TABLE 13 Breakdown Glass strength/std Dissipation Energy TransitionPoly- dev Dielectric Factor Density Temp mer (V/micron) constant(***)(%)(***) (J/cc) (° C.) PC1 804/99 3.05 0.35 8.7 152 CPC1 738/178 3.230.71 7.8 196 CPC2 801/165 3.2 0.33 9.1 140 CPC3 636/75 3.5 0.82 6.3 136CPC4 660/95 3.3 0.65 6.4 141 CPC5 766/149 3.55 0.96 9.2 177 CPC6 692/1493.22 0.37 6.8 171 (***)These tests were conducted on compression moldedsamples prepared as described in the procedure above.

The copolyestercarbonates demonstrated high average values for BreakdownStrength (˜650-800 V/micron). The Dielectric Constant values for thecopolyestercarbonates were uniformly equal to or better than PC1, apolycarbonate evaluated above. Three coplyestercarbonates, CPC1, CPC5,and CPC6 demonstrated excellent overall performance on the electricalproperties and exhibited high Tg values and were further evaluated forfilm properties, below.

Surface Roughness of Extrusion Films—Films of CPC1, CPC5 and CPC6 wereevaluated as described in the procedure above, and the results are shownon Table 14 a, and 14 b, below, on which the values reported are inmicrons.

TABLE 14a Film Side 1 Ra Side 2 Ra Side 1 + Side 2 Ra CPC5 0.0266 0.00560.0490 0.0011 0.0378 0.0128 CPC6 0.0117 0.0037 0.0173 0.0082 0.01450.0065 CPC1 0.0056 0.0005 0.0089 0.0043 0.0073 0.0033

TABLE 14b Film Side 1 Rq Side 2 Rq Side 1 + Side 2 Rq CPC5 0.0346 0.00700.0707 0.0054 0.0526 0.0346 CPC6 0.0164 0.0061 0.0224 0.0100 0.01940.0164 CPC1 0.0077 0.0012 0.0112 0.0054 0.0095 0.0077

These results showed that the average roughness values were under 0.04microns for both sides.

Table 15 shows the dielectric breakdown strength of the film of CPC1 at20 sites on the film.

TABLE 15 Breakdown Breakdown Thickness Voltage Strength Site (micron)(k-VDC) (V/micron)  1 11.5 12.44 1081  2 11.5 10.09 874  3 12.3 10.55857  4 10.3 9.25 898  5 11.4 10.54 925  6 9.50 8.65 911  7 9.13 6.72 736 8 7.42 7.62 1027  9 7.81 7.15 916 10 7.79 7.46 957 11 8.91 6.74 756 1211.1 8.03 721 13 10.0 8.63 860 14 8.83 9.83 1113 15 8.51 8.00 941 169.06 8.02 885 17 12.4 11.19 902 18 11.5 11.56 1004 19 10.8 10.51 973 2010.0 10.37 1036 Mean 10.00 9.17 919 StDev 1.54 1.70 106

These results showed that the film of CPC1 had an average breakdownstrength in excess of 900 V/micron with a standard deviation of 106V/micron and failed at an average voltage of about 9,170 VDC.

Table 16 shows the dielectric breakdown strength of the film of CPC5 at20 sites on the film.

TABLE 16 Breakdown Breakdown Thickness Voltage Strength Site (micron)(k-VDC) (V/micron)  1 10.7 11.85 1107  2 10.9 10.06 927  3 11.2 10.56945  4 10.6 11.19 1061  5 8.30 9.27 1117  6 10.7 6.73 627  7 7.36 9.181247  8 9.16 9.27 1012  9 9.30 8.03 864 10 10.5 7.85 748 11 13.9 10.49753 12 8.08 8.63 1068 13 8.82 8.64 980 14 9.15 7.12 778 15 8.17 8.581050 16 9.99 12.46 1248 17 13.5 10.46 777 18 9.70 9.27 956 19 10.0 10.541052 20 10.4 8.01 773 Mean 10.01 9.41 955 StDev 1.65 1.53 172

These results showed that the film of CPC1 had an average breakdownstrength in excess of 900 V/micron with a standard deviation of 172V/micron and failed at an average voltage of about 9,410 VDC.

Table 17 shows the dielectric breakdown strength of the film of CPC6 at20 sites on the film.

TABLE 17 Breakdown Breakdown Thickness Voltage Strength Site (micron)(k-VDC) (V/micron)  1 7.16 6.08 849  2 9.77 8.61 881  3 11.1 9.24 834  410.3 8.54 829  5 8.00 7.39 924  6 8.43 6.73 798  7 10.3 10.52 1022  811.1 9.24 832  9 12.7 11.28 891 10 15.0 15.16 1009 11 15.6 15.68 1008 1215.0 13.09 873 13 16.1 13.08 811 14 14.0 6.75 484 15 11.2 10.53 939 169.50 8.63 908 17 7.67 6.71 875 18 9.20 5.41 588 19 8.26 6.15 744 20 10.48.31 796 Mean 11.04 9.36 845 StDev 2.79 3.01 130

These results showed that the film of CPC1 had an average breakdownstrength in excess of 840 V/micron with a standard deviation of 130V/micron and failed at an average voltage of about 9,360 VDC.Advantageously, films made in accordance to our invention exhibited athickness of more than 0 and less than 7 micrometers, a variation of thethickness of the film of +/−10% or less of the thickness of the film, asurface roughness average of less than +/−3% of the average thickness ofthe film as measured by optical profilometry; a dielectric constant at 1kHz and room temperature of at least 2.7; a dissipation factor at 1 kHzand room temperature of 1% or less; and a breakdown strength of at least300 Volt/micrometer.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety.

Although the present invention has been described in detail withreference to certain preferred versions thereof, other variations arepossible. Therefore, the spirit and scope of the appended claims shouldnot be limited to the description of the versions contained therein.

1. A uniaxially-stretched, extruded film comprising a polycarbonate,wherein the film has at least one wrinkle-free region having a firstsurface and a second surface, the at least one extruded wrinkle-freeregion comprising: a thickness of more than 0 and less than 7micrometers, and a variation of the thickness of the film of +/−10% orless of the thickness of the film, and a surface roughness average ofless than +/−3% of the average thickness of the film as measured byoptical profilometry; and further wherein the film has: a dielectricconstant at 1 kHz and room temperature of at least 2.7; a dissipationfactor at 1 kHz and room temperature of 1% or less; and a breakdownstrength of at least 300 Volt/micrometer.
 2. The film of claim 1,wherein the film has a length of at least 10 meter, and a width of atleast 300 millimeter, and at least 80% of the area of the film is thewrinkle-free region.
 3. The film of claim 1, wherein the film has anenergy density of at least 3 J/cc.
 4. The film of claim 2, wherein thefilm has a length of 100 to 10,000 meter, and a width of 300 to 3,000millimeter.
 5. The film of claim 1, wherein the film has less than 1,000ppm of a compound having a molecular weight of less than 250 Dalton. 6.The film of claim 1, wherein the film has less than 50 ppm each ofaluminum, calcium, magnesium, iron, nickel, potassium, manganese,molybdenum, sodium, titanium, and zinc.
 7. The film of claim 1,comprising less than 1000 ppm each of a fluorine-containing compound ora silicone-containing compound.
 8. The film of claim 1, comprising lessthan 100 ppm of a fluorine-containing compound or a silicone-containingcompound.
 9. The film of claim 1, wherein the film has no observablespecks or gels over an area of at least 3 square meter when viewed at adistance of 0.3 meter without magnification.
 10. The film of claim 1,wherein the film has no observable voids over an area of at least 3square meter when viewed at a magnification of 50×.
 11. The film ofclaim 1, wherein at least one of the surfaces of the wrinkle-free regionhas a roughness value Ra of less than 3% of the average thickness of thefilm.
 12. The film of claim 1, wherein the polycarbonate is apolycarbonate having repeating structural carbonate units of formula (1)

in which at least 60 percent of the total number of R¹ groups containaromatic moieties and the balance thereof are aliphatic, alicyclic, oraromatic.
 13. The film of claim 12, wherein the polycarbonate is ahomopolycarbonate derived from polymerization of a bisphenol compound(3)

wherein R^(a) and R^(b) are each independently a halogen atom or amonovalent hydrocarbon group; p and q are each independently integers of0 to 4; and X^(a) is a bridging group connecting the twohydroxy-substituted aromatic groups, where the bridging group and thehydroxy substituent of each C₆ arylene group are disposed ortho, meta,or para (specifically para) to each other on the C₆ arylene group. 14.The film of claim 13, wherein each X^(a) is independently selected froma single bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, and a C₁₋₁₈ organicgroup.
 15. The film of claim 13, wherein each X^(a) is independentlyselected from a C₁₋₁₈ alkylene group, a C₃₋₁₈ cycloalkylene group, afused C₆₋₁₈ cycloalkylene group, a group of the formula —B¹—W—B²—wherein B¹ and B² are the same or different C₁₋₆ alkylene group and W isa C₃₋₁₂ cycloalkylidene group or a C₆₋₁₆ arylene group; analkyl-substituted bisphenol (4)

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, R^(g) isC₁₋₁₂ alkyl or halogen, r and s are each independently 1 to 4, and t is0 to 10; and a substituted C₃₋₁₈ cycloalkylidene (5)

wherein R^(r), R^(p), R^(q), and R^(t) are independently hydrogen,halogen, oxygen, or C₁₋₁₂ organic groups; I is a direct bond, a carbon,or a divalent oxygen, sulfur, or —N(Z)— where Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 1or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with theproviso that at least two of R^(r), R^(p), R^(q), and R^(t) takentogether are a fused cycloaliphatic, aromatic, or heteroaromatic ring.16. The film of claim 13, wherein the C₁₋₁₈ organic bridging group is—C(R^(c))(R^(d))— or —C(═R^(e))—, wherein R^(c) and R^(d) are eachindependently a hydrogen atom or a monovalent C₁₋₆ linear or cyclichydrocarbon group and R^(e) is a divalent hydrocarbon group, p and q iseach 0 or 1, and R^(a) and R^(b) are each a C₁₋₃ alkyl group
 17. Thefilm of claim 13, wherein the bisphenol compound (3) is selected from1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane,2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane,1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl)propane, 1,1-bis(4-hydroxy-t-butylphenyl) propane,3,3-bis(4-hydroxyphenyl) phthalimidine,2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine, and1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane.
 18. The film of claim 12,wherein the polycarbonate is a homopolymer.
 19. The film of claim 12,wherein the polycarbonate is copolycarbonate comprising at least twodifferent R¹ moieties.
 20. The film of claim 12, wherein thepolycarbonate is a polycarbonate copolymer comprising a repeatingcarbonate unit (1), and a repeating unit selected from ester units,diorganosiloxane units, urethane units, arylene ether units, arylenesulfone units, arylene ketone units, and combinations thereof.
 21. Thefilm of claim 20 wherein the polycarbonate is a poly(carbonate-ester)comprising repeating carbonate units (1), and repeating ester units (7)

wherein J is selected from a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclicgroup, a C₆₋₂₀ aromatic group, and a polyoxyalkylene group in which thealkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4carbon atoms; and T is selected from a C₂₋₁₀ alkylene group, a C₆₋₂₀alicyclic group, a C₆₋₂₀ alkyl aromatic group, or a C₆₋₂₀ aromaticgroup.
 22. The film of claim 21, wherein the poly(carbonate-ester)comprises repeating aromatic carbonate-ester units (8)

wherein Ar is divalent aromatic residue of a dicarboxylic acid orcombination of dicarboxylic acids, and Ar′ is a divalent aromaticresidue of (a) a bisphenol (3)

wherein R^(a) and R^(b) are each independently a halogen atom or amonovalent hydrocarbon group; p and q are each independently integers of0 to 4; and X^(a) is a bridging group connecting the twohydroxy-substituted aromatic groups, where the bridging group and thehydroxy substituent of each C₆ arylene group are disposed ortho, meta,or para (specifically para) to each other on the C₆ arylene group, or(b) an aromatic dihydric compound (6)

wherein each R^(h) is independently a halogen atom, a C₁₋₁₀ hydrocarbylgroup, a halogen-substituted C₁₋₁₀ alkyl group, a C₆₋₁₀ aryl group, or ahalogen-substituted C₆₋₁₀ aryl group, and n is 0 to 4; and x is 20 toless than 100 and y is more than 0 to 80, wherein x and y are in partsby weight based on 100 parts by weight of the poly(carbonate-ester). 23.The film of claim 22, wherein Ar is the residue of isophthalic acid(9a), terephthalic acid (9b),

or a combination thereof.
 24. The film of claim 23, wherein Ar′ is theresidue of bisphenol A.
 25. The film of claim 21, wherein thepolycarbonate is a poly(carbonate-ester) comprising repeating carbonateunits (1) derived from a bisphenol (3)

wherein R^(a) and R^(b) are each independently a halogen atom or amonovalent hydrocarbon group; p and q are each independently integers of0 to 4; and X^(a) is a bridging group connecting the twohydroxy-substituted aromatic groups, where the bridging group and thehydroxy substituent of each C₆ arylene group are disposed ortho, meta,or para (specifically para) to each other on the C₆ arylene group; andrepeating arylate ester units (9)

wherein each R⁴ is independently a halogen or a C₁₋₄ alkyl, and p is 0to
 3. 26. The film of claim 25, wherein the ester units arepoly(isophthalate-terephthalate-resorcinol ester) units.
 27. The film ofclaim 26, wherein the bisphenol (3) is bisphenol A.
 28. The film ofclaim 25, wherein the poly(carbonate-ester) further comprises repeatingcarbonate units (1) derived from an aromatic dihydric compound (6)

wherein each R⁴ is independently a halogen or a C₁₋₄ alkyl, and n is 0to 3; and wherein the molar ratio of carbonate units derived frombisphenol (3) to carbonate units derived from dihydroxy compound (6) is1:99 to 99:1.
 29. The film of claim 28, wherein the ester units arepoly(isophthalate-terephthalate-resorcinol ester) units.
 30. The film ofclaim 29, wherein the poly(carbonate-ester) is a poly(bisphenol-Acarbonate)-co-(resorcinolcarbonate)-co(isophthalate-terephthalate-resorcinol ester).
 31. The filmof claim 19, wherein the polycarbonate is a poly(carbonate-siloxane)comprising repeating carbonate units (1); and repeating diorganosiloxaneunits (10)

wherein each R is independently the same or different C₁₋₁₃ monovalentorganic group; and E has an average value of 5 to
 200. 32. The film ofclaim 31, wherein the polysiloxane units are of formula (13):

wherein each R is independently the same or different C₁₋₁₃ monovalentorganic group; E has an average value of 5 to 65; R⁶ is a divalent C₂-C₈aliphatic group; each M is independently a halogen, cyano, nitro, C₁-C₈alkylthio, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxygroup, C₃-C₈ cycloalkyl, C₃-C₈ cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy,C₇-C₁₂ aralkyl, C₇-C₁₂ aralkoxy, C₇-C₁₂ alkylaryl, or C₇-C₁₂alkylaryloxy; and each n is independently 0, 1, 2, 3, or
 4. 33. The filmof claim 32, wherein in the carbonate units, R¹ is derived frombisphenol A; and in the siloxane units, M is methoxy, n is one, R² is adivalent C₁-C₃ aliphatic group, and R is methyl.
 34. The film of claim19, wherein the polycarbonate is a polycarbonate-ester-siloxane)comprising repeating carbonate units (1); repeating siloxane units (10)

wherein each R is independently the same or different C₁₋₁₃ monovalentorganic group; and E has an average value of 5 to 200; and repeatingester units (7)

wherein J is selected from a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclicgroup, a C₆₋₂₀ aromatic group, and a polyoxyalkylene group in which thealkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4carbon atoms; and T is selected from a C₂₋₁₀ alkylene group, a C₆₋₂₀alicyclic group, a C₆₋₂₀ alkyl aromatic group, or a C₆₋₂₀ aromaticgroup.
 35. The film of claim 3, wherein in the polycarbonate units, R¹is derived from a bisphenol A; the siloxane units are polysiloxaneblocks (13):

wherein each R is independently the same or different C₁₋₁₃ monovalentorganic group; E has an average value of 5 to 65; R⁶ is a divalent C₂-C₈aliphatic group; each M is independently a halogen, cyano, nitro, C₁-C₈alkylthio, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxygroup, C₃-C₈ cycloalkyl, C₃-C₈ cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy,C₇-C₁₂ aralkyl, C₇-C₁₂ aralkoxy, C₇-C₁₂ alkylaryl, or C₇-C₁₂alkylaryloxy; and each n is independently 0, 1, 2, 3, or 4; and theester units are of formula (9)

wherein each R⁴ is independently a halogen or a C₁₋₄ alkyl, and p is 0to
 3. 36. The film of claim 34, wherein in the carbonate units, R¹ isderived from bisphenol A; in the polysiloxane blocks, M is methoxy, n isone, R² is a divalent C₁-C₃ aliphatic group, and R is methyl; and theester units are (isophthalate-terephthalate-resorcinol) ester units 37.An article comprising the film of claim
 1. 38. The article of claim 37,further comprising a layer of a conductive metal deposited on at least aportion of the wrinkle-free region.
 39. The article of claim 38, whereinthe conductive metal comprises aluminum, zinc, copper, or a combinationthereof.
 40. The article of claim 39, wherein the conductive metal layerhas a thickness of 1 to 3000 Angstroms.
 41. The article of claim 40,wherein the conductive metal layer has a thickness of 1 to 2000Angstroms.
 42. The article of claim 41, wherein the conductive metallayer has a resistivity of 0.1 to 100 Ohm/sq.
 43. The article of claim38, wherein the conductive metal layer is deposited by chemical vapordeposition, high temperature vacuum operations, or combinations thereof.44. A capacitor comprising a wound, metallized film of claim
 37. 45. Anelectronic article comprising the capacitor of claim
 44. 46. The film ofclaim 1 wound on a roll, wherein the roll has no observable wrinkles ordie lines when viewed without magnification at a distance of 0.3 meter.47. An article comprising a portion of the film of claim
 46. 48. Thearticle of claim 47, further comprising a layer of a conductive metaldeposited on at least a portion of the surface of the wrinkle-freeregion.
 49. The article of claim 48, wherein the conductive metalcomprises aluminum, zinc, copper, or a combination thereof.
 50. Thearticle of claim 49, wherein the conductive metal layer has a thicknessof 1 to 1000 angstrom.
 51. The article of claim 50, wherein theconductive metal layer has a resistivity of 0.1 to 100 Ohm/sq.
 52. Thearticle of claim 48, wherein the conductive metal layer is deposited bychemical vapor deposition, high temperature vacuum operations, orcombinations thereof.
 53. A capacitor comprising a wound metallized filmof claim
 46. 54. An electronic article comprising the capacitor of claim53.